For 2011 Pic moved to the Barwa Addax squad alongside future Formula 1 team-mate Giedo van der Garde.[7] Despite failing to score any points in the preceding Asia Series campaign, he hit back with a second career GP2 win at Catalunya where he led home Van der Garde for an Addax one-two finish. Another victory, this time on the streets of Monaco, helped move him up to third place in the drivers' championship. The two points he then scored for taking pole position at Valencia briefly moved Pic into the championship lead but, after retiring from both races and dropping back in the standings as a result, he eventually finished the season fourth overall, three points clear of Van der Garde.[6]

In November 2011 Pic made his debut at the wheel of a Formula One car, driving for Marussia Virgin Racing at the young driver test held at Yas Marina Circuit in Abu Dhabi.[8] He was due to drive for a day and-a-half of the test, but the Virgin team decided to give him a further half-day of running after he encountered engine problems on the second day of the test.[9]

In November 2012 it was announced that Pic had signed a multi-year contract at the Renault-powered Caterham squad, with former GP2 team-mate and F1 rookie Giedo van der Garde later confirmed alongside him.

His season began to gather pace in Bahrain where Pic comfortably beat both Marussia cars and a Sauber, before a major upgrade to his Caterham at the Spanish Grand Prix established Pic as the quickest of the younger teams' drivers. He would continue this trend throughout the European portion of the season, scoring 15th-place finishes at Silverstone and the Hungaroring while displaying pace close to that of the established midfield runners.

Pic recovered well at the season-closing Brazilian Grand Prix, where he qualified over half a second clear of team-mate van der Garde and well clear of the Marussias. However his race ended early when a suspension failure forced him into retirement on lap 58.

On 21 January 2014, Caterham's Team Principal Cyril Abiteboul confirmed that Pic would not be driving for Caterham in 2014:

Unfortunately Charles won't be with us next season. It's a pity that the adventure between Caterham and Charles is ending. On a personal level I want to thank Charles for the work he achieved last year.

^Bean, David (21 November 2011). "Brazilian Grand Prix 2011: Preview". TheCheckeredFlag.co.uk. BlackEagleMedia. Retrieved 22 November 2011. Brazil could also be the final race for Jérôme d'Ambrosio, with Virgin Racing expected to announce Charles Pic alongside Timo Glock for next season.